Methods of forming devices including multi-portion liners

ABSTRACT

A method of forming a semiconductor structure. The method comprises forming a protective portion of a liner on at least a portion of stack structures on a substrate. The protective portion comprises a material formulated to adhere to the stack structures. A conformal portion of the liner is formed on the protective portion of the liner or on the protective portion of the liner and exposed materials of the stack structures. At least one of the protective portion and the conformal portion does not comprise aluminum. Additional methods of forming a semiconductor structure are disclosed, as are semiconductor structures including the liners comprising the protective portion and the conformal portion.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/110,760, filed Aug. 23, 2018, now U.S. Pat. No. 10,665,782, issuedMay 26, 2020, which is a continuation of U.S. patent application Ser.No. 14/244,486, filed Apr. 3, 2014, now U.S. Pat. No. 10,249,819, issuedApr. 2, 2019, the disclosure of which is hereby incorporated herein itits entirety by this reference.

This application is also related to U.S. patent application Ser. No.15/857,873, filed Dec. 29, 2017, now U.S. Pat. No. 10,658,580, issuedMay 19, 2020, entitled SEMICONDUCTOR STRUCTURES INCLUDING MULTI-PORTIONLINERS, to U.S. patent application Ser. No. 14/189,323, filed Feb. 25,2014, now U.S. Pat. No. 9,484,196, issued Nov. 1, 2016, and entitledSEMICONDUCTOR STRUCTURES INCLUDING LINERS COMPRISING ALUCONE AND RELATEDMETHODS, to U.S. patent application Ser. No. 14/189,265, filed Feb. 25,2014, now U.S. Pat. No. 9,577,010, issued Feb. 21, 2017, and entitledCROSS-POINT MEMORY AND METHODS FOR FABRICATION OF SAME, and to U.S.patent application Ser. No. 14/189,490, filed Feb. 25, 2014, now U.S.Pat. No. 9,806,129, issued Oct. 31, 2017, and entitled CROSS-POINTMEMORY AND METHODS FOR FABRICATION OF SAME, the disclosure of each ofwhich is hereby incorporated herein it its entirety by this reference.

FIELD

Embodiments disclosed herein relate to semiconductor structuresincluding memory cells having liner materials and methods of formingsuch semiconductor structures. More specifically, embodiments disclosedherein relate to semiconductor structures for increasing memory densityand methods of forming such semiconductor structures.

BACKGROUND

Due to rapid growth in use and application of digital informationtechnology, there are demands to continuingly increase the memorydensity of memory devices while maintaining, if not reducing, the sizeof the devices. Three-dimensional (3D) structures have been investigatedfor increasing the memory density of a device. For example, 3Dcross-point memory cells have been investigated as devices havingincreased capacity and smaller critical dimensions. These 3Dsemiconductor structures typically include stacks of materials on asubstrate. The materials include phase change materials, switching diodeelements, charge storage structures (e.g., floating gates, charge traps,tunneling dielectrics), and charge blocking materials between the chargestorage structures and adjacent control gates.

Fabricating these 3D structures often requires forming high aspect ratiofeatures from the stacks of materials. Frequently, materials that aresensitive to downstream processing conditions are present in the stacks.For example, stacks in 3D cross-point memory cells may includematerials, such as chalcogenide materials, carbon-containing electrodes,and other sensitive materials that may be damaged at the temperaturesused during conventional semiconductor fabrication processes or mayreact with etchants used during downstream processing. For instance,chalcogenide materials in the stacks may volatilize during conventionaldeposition techniques, causing delamination of the stack materials. Toprotect the stacks, liners have been formed over the materials of thestack before the subsequent processing acts are conducted. In order toprevent damage to the materials of the stacks, a liner must be formed bya highly conformal deposition technique and must be formed using gentledeposition conditions. In addition, the liner must be formed of a highquality material. The liner must also adhere to the different materialsof the stacks. Conventional liners, which are formed of a singlematerial, such as silicon oxide or silicon nitride, do not meet theserequirements because gentle deposition conditions and good adhesion aretypically at odds with high quality and high conformality becausedeposition techniques that produce high quality, highly conformalmaterials damage chalcogenide materials of the stack and degradeadhesion. Conventional techniques for improving the step coverage andquality of the single material liners damage chalcogenide materials anddegrade adhesion. Therefore, it would be desirable to produce a highquality, highly conformal liner that is formed under gentle depositionconditions and provides good adhesion to the underlying materials.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B are simplified cross-sectional views of a lineraccording to some embodiments of the present disclosure on materials ofa stack; and

FIGS. 2A-2G are simplified cross-sectional views of a 3D semiconductorstructure at various stages of processing, the semiconductor structureincluding a liner according to some embodiments of the presentdisclosure.

DETAILED DESCRIPTION

The illustrations included herewith are not meant to be actual views ofany particular systems or memory structures, but are merely idealizedrepresentations that are employed to describe embodiments describedherein. Elements and features common between figures may retain the samenumerical designation except that, for ease of following thedescription, for the most part, reference numerals begin with the numberof the drawing on which the elements are introduced or most fullydiscussed.

The following description provides specific details, such as materialtypes, material thicknesses, and processing conditions in order toprovide a thorough description of embodiments described herein. However,a person of ordinary skill in the art will understand that theembodiments disclosed herein may be practiced without employing thesespecific details. Indeed, the embodiments may be practiced inconjunction with conventional fabrication techniques employed in thesemiconductor industry. In addition, the description provided hereindoes not form a complete process flow for manufacturing 3D semiconductorstructures, and the semiconductor structures described below do not forma complete semiconductor device. Only those process acts and structuresnecessary to understand the embodiments described herein are describedin detail below. Additional acts to form complete semiconductor devicesincluding the semiconductor structures described herein may be performedby conventional techniques.

The present disclosure relates to a multi-portion liner, a portion ofwhich is formulated to protect underlying materials of stacks on asubstrate, while at least another portion of the liner is a highlyconformal, high quality material. The liner includes at least twoportions, the portion that protects and adheres to at least a portion ofthe stack, which is referred to herein as the protective portion or theprotective material, and another portion that provides a high degree ofconformality and quality to the liner, which is referred to herein asthe conformal portion or conformal material. In addition to protectingthe materials of the stacks from heat or chemical damage, the protectiveportion may be formulated to provide adhesion between the materials ofthe stacks and the conformal portion of the liner. The degree ofprotection provided by the protective portion of the liner may besufficient to prevent intermixing or migration of chalcogenide materialsfrom the stacks. The degree of adhesion provided by the protectiveportion of the liner may be sufficient for the conformal portion of theliner to adhere to the materials of the stacks. The conformal portionmay be formed on the protective portion to provide good step coverage(e.g., conformality) and quality to the liner. As used herein, the term“step coverage” means and includes a ratio of a thickness of a materialover a step edge to the thickness of the material on a flat surface. Asused herein, the term “quality” means and includes the density, wet etchrate, and barrier property of the material. While embodiments of theliner are described and illustrated herein as having two portions, theliner may include more than two portions, the combination of which mayachieve the desired adhesion, protective, step coverage, and filmquality characteristics.

The liner may be a continuous film on the stacks or on a portion of thestacks, protecting the materials of the stacks from heat or chemicaldamage and functioning as a seal (e.g., an encapsulant) around thematerials of the stacks. As used herein, the term “continuous” means andincludes a material having substantially no interruptions, such asvoids, gaps, pinholes, or other openings, therein, at least in regionswhere and/or for the processing acts during which it is intended toprotect, seal, or encapsulate the materials of the stack. The liner mayinclude the protective portion on (i.e., in direct contact with) thematerials of the stacks, while the conformal portion is on (i.e., indirect contact with) the protective portion. The protective portion maybe formed on at least a portion of the stacks such as on materials ofthe stacks that are heat sensitive or sensitive to chemical damage. Insome embodiments, such as that of FIG. 1A, the protective portion 110 aof the liner 110 is formed on substantially all the materials of thestacks 105, such that the protective portion 110 a forms a continuousmaterial on the stacks 105. The conformal portion 110 b is then formedon the protective portion 110 a. In other embodiments, as shown in FIG.1B, the protective portion 110 a′ is formed on only a portion of thestacks 105, such as on sensitive materials of the stacks 105. In suchsituations, the protective portion 110 a′ of the liner 110′ may be indirect contact with only certain materials of the stacks 105, such asmaterials sensitive to heat or chemical damage. The protective portion110 a′ may form a continuous material on the desired portion of thestacks 105. The conformal portion 110 b′ is then formed over theprotective portion 110 a′ and exposed regions of the stacks 105.

As explained in more detail below, the stacks 105 may include aconductive feature 130 on a substrate (not shown), a bottom electrode140 on the conductive feature 130, a switching diode element 150 (e.g.,a diode or an ovonic threshold switch) on the bottom electrode 140, amiddle electrode 160 on the switching diode element 150, an activestorage element 170 on the middle electrode 160, and a top electrode 180on the active storage element 170. In some embodiments, only a subset ofthe features, elements, and/or electrodes may be present. The conductivefeature 130 may be configured as a conductive line, such as an accessline (e.g., a word line) or a digit line (e.g., a bit line). While asingle stack is illustrated in FIGS. 1A and 1B, multiple stacks 105 maybe present and separated from one another by openings (not shown). Thestacks 105 may have an aspect ratio of up to about 15:1.

The protective portion 110 a, 110 a′ and the conformal portion 110 b,110 b′ of the liner 110, 110′ may be formed from at least one dielectricmaterial, with the dielectric material of each portion selected tocontribute different properties to the liner 110, 110′. The protectiveportion 110 a, 110 a′ may provide protection of and adhesion to theunderlying materials of the stacks 105, and the conformal portion 110 b,110 b′ may provide the desired degree of conformality and quality to theliner 110, 110′. Since the protective portion 110 a, 110 a′ providesadhesion between the conformal portion 110 b, 110 b′ and the materialsof the stacks 105, the dielectric material of the protective portion 110a, 110 a′ may have a higher degree of adhesion to the materials of thestacks 105 than that of the conformal portion 110 b, 110 b′. Since theconformal portion 110 b, 110 b′ provides the desired degree ofconformality and quality to the liner 110, 110′, the quality andconformality of the conformal portion 110 b, 110 b′ may be higher thanthe quality and conformality of the protective portion 110 a, 110 a′.

The dielectric material of the protective portion 110 a, 110 a′ mayadhere to the materials of the stacks 105, such as to chalcogenide orcarbon materials of the stacks 105. The protective portion 110 a, 110 a′of the liner 110, 110′ may be formed by a technique that does not damageor degrade the materials of the stacks 105. The protective portion 110a, 110 a′ may be formed by a low temperature process, such as a processconducted at a temperature of less than about 250° C., reducing thelikelihood of heat damage to the materials of the stacks 105. By way ofexample only, the protective portion 110 a, 110 a′ may be formed by alow temperature, chemical vapor deposition (CVD) process, such as acapacitively coupled plasma enhanced chemical vapor deposition (PECVD)process, an inductively coupled plasma chemical vapor deposition(ICPCVD) process, a pulsed CVD process, or a remote plasma CVD process.The low temperature process for forming the protective portion 110 a,110 a′, if PECVD is employed, may be conducted with or without pulsingof the process power source.

In some embodiments, the protective portion 110 a, 110 a′ is siliconnitride (SiN). As used herein, the term “silicon nitride” means andincludes a chemical compound including silicon atoms and nitrogen atoms,and includes stoichiometric and non-stoichiometric compounds of siliconand nitrogen, as well as a gradient of nitrogen atoms in the silicon.The SiN is formed by a pulsed PECVD process conducted at a temperatureof less than about 250° C. The PECVD process may utilize conventionalsilicon reactant gases that do not contain carbon and conventionalnitrogen reactant gases. For instance, the SiN may be formed usingsilane (SiH₄) and ammonia (NH₃) or silane and nitrogen gas (N₂) as thereactant gases. Other parameters of the PECVD process, such as flowrates, pressure, and RF power may be determined by a person of ordinaryskill in the art and are not described in detail herein. The PECVDprocess may also be free of chlorinated reagents or plasma treatments toreduce or prevent chemical damage or heat damage to the materials of thestacks 105.

In other embodiments, the protective portion 110 a, 110 a′ of the liner110, 110′ is formed of aluminum oxide (AlO_(x)). The AlO_(x) may beformed by conventional techniques, such as PECVD, which are notdiscussed in detail herein. By way of example only, the aluminum oxidemay be formed by a low temperature atomic layer deposition process bypulsing aluminum precursors and oxygen containing precursorssequentially.

The protective portion 110 a, 110 a′ may be formed at a thicknesssufficient to protect the materials of the stacks 105 from heat orchemical damage. The protective portion 110 a, 110 a′ may be formed to adesired thickness, such as from about 10 Å to about 30 Å or from about15 Å to about 25 Å. Alternatively, the protective portion 110 a, 110 a′may be formed to a greater initial thickness and a portion of itsthickness removed to produce the desired thickness of the protectiveportion 110 a, 110 a′. The protective portion 110 a, 110 a′ may beformed on the stacks 105 at a single (i.e., substantially uniform)thickness, or the protective portion 110 a, 110 a′ may vary in thicknessdepending on its location on the stacks 105. If, for example, theprotective portion 110 a′ is formed on only a portion of the stacks 105(see FIG. 1B), such as only on materials of the stacks 105 that are heatsensitive or sensitive to chemical damage, the thickness of theprotective portion 110 a′ on a horizontal surface of the stacks 105 andupper sidewalls of the stacks 105 may be greater than the thickness onlower sidewalls of the stacks 105. By way of example only, the thicknessof the protective portion 110 a′ on the horizontal surface and on theupper sidewalls of the stacks 105 may be about 25 Å and may graduallydecrease to a thickness of about 0 Å along sidewalls of the bottoms ofthe stacks 105.

The conformal portion 110 b, 110 b′ may be formed on the protectiveportion 110 a, 110 a′ and any exposed portions of the materials of thestacks 105 as a continuous material, as shown in FIGS. 1A and 1B. Thus,the conformal portion 110 b, 110 b′ may seal the materials of the stacks105, providing low leakage and good electrical performance to memorycells including the stacks 105. The conformal portion 110 b, 110 b′ mayalso be resistant to oxidation. The dielectric material of the conformalportion 110 b, 110 b′ may be selected to provide good step coverage andquality to the liner 110, 110′. The dielectric material of the conformalportion 110 b, 110 b′ may be formed of SiN, silicon oxynitride (SiON),silicon carbonitride (SiCN), silicon carboxynitride (SiOCN), or silicondioxide (SiO₂). As used herein, the term “silicon oxynitride” means andincludes a chemical compound including silicon atoms, nitrogen atoms,and oxygen atoms, and includes stoichiometric and non-stoichiometriccompounds of silicon, nitrogen, and oxygen, as well as a gradient ofnitrogen and oxygen atoms in the silicon. As used herein, the term“silicon carbonitride” means and includes a chemical compound includingsilicon atoms, carbon atoms, and nitrogen atoms, and includesstoichiometric and non-stoichiometric compounds of silicon, carbon, andnitrogen, as well as a gradient of nitrogen and carbon atoms in thesilicon. As used herein, the term “silicon carboxynitride” means andincludes a chemical compound including silicon atoms, carbon atoms,nitrogen atoms, and oxygen atoms, and includes stoichiometric andnon-stoichiometric compounds of silicon, carbon, nitrogen, and oxygen,as well as a gradient of nitrogen, carbon, and oxygen atoms in thesilicon.

In other embodiments, the dielectric material of the conformal portion110 b, 110 b′ may be formed of aluminum oxide (AlO_(x)). The aluminumoxide (AlO_(x)) as the conformal portion 110 b, 110 b′ may be formedover a non-aluminum containing protective portion 110 a, 110 a′.

In yet other embodiments, the protective portion 110 a, 110 a′ and theconformal portion 110 b, 110 b′ may be formed of SiCN, where the SiCN ofthe protective portion 110 a, 110 a′ includes a lower amount of carbonthan the SiCN of the conformal portion 110 b, 110 b′.

Since any sensitive materials of the stacks 105 are protected by theprotective portion 110 a, 110 a′, formation of the conformal portion 110b, 110 b′ of the liner 110, 110′ may utilize more aggressive chemistriesor techniques than would be possible if the protective portion 110 a,110 a′ was not present, as described in more detail below. Formation ofthe conformal portion 110 b, 110 b′ may also, optionally, include plasmaor heat treatments, as described in more detail below, since anysensitive materials of the stacks 105 are protected by the protectiveportion 110 a, 110 a′. Thus, the conformal portion 110 b, 110 b′ may beformed with fewer processing constraints than if the protective portion110 a, 110 a′ was not present.

The dielectric material of the conformal portion 110 b, 110 b′ of theliner 110, 110′ may be formed by a deposition technique that conformallyforms the dielectric material on the protective portion 110 a, 110 a′.The dielectric material of the conformal portion 110 b, 110 b′ may beformed by an atomic layer deposition (ALD) process that provides thedesired conformality and quality, or an ALD-like process, such as pulsedCVD, remote plasma CVD, or PECVD. However, other processes may be used,such as a CVD process or a physical vapor deposition (PVD) process, withsubsequent optional treatment acts conducted to improve the quality ofthe conformal portion 110 b, 110 b′ and, thus, the quality of the liner110, 110′. The precursors or reactant gases used to form the conformalportion 110 b, 110 b′ may be selected by a person of ordinary skill inthe art and, thus, are not described in detail herein. Other parametersof the process for forming the conformal portion 110 b, 110 b′, such asflow rates, pressure, and RF power, may be determined by a person ofordinary skill in the art and are not described in detail herein.

The optional treatment of the conformal portion 110 b, 110 b′ mayinclude, but is not limited to, a plasma treatment, a heat treatment, oran ultraviolet (UV) treatment. The conformal portion 110 b, 110 b′ ofthe liner 110, 110′ may also, optionally, be modified or subjected to exsitu treatments to improve the quality of the liner 110, 110′. Forinstance, a total desired thickness of the conformal portion 110 b, 110b′ may be formed by the CVD process or PVD process and subjected to aplasma treatment, heat treatment, or UV treatment to increase thequality of the conformal portion 110 b, 110 b′. Alternatively, a desiredthickness of the conformal portion 110 b, 110 b′ may be formed by theCVD process or PVD process, and the resulting thickness subjected to theplasma treatment or heat treatment, followed by additional depositionand treatment acts until the conformal portion 110 b, 110 b′ is of thetotal desired thickness. Thus, if the initial quality of an as-formedthickness of the conformal portion 110 b, 110 b′ of the liner 110, 110′is not sufficient, the quality may be improved by subjecting thethickness of the conformal portion 110 b, 110 b′ to the plasma treatmentor heat treatment. The plasma treatment or heat treatment may densifythe conformal portion 110 b, 110 b′ of the liner 110, 110′, improvingits quality. The plasma treatment may include, but is not limited to,treatment with helium in a nitrogen (N₂) plasma or treatment with argonin a nitrogen (N₂) plasma. The plasma may be a direct plasma or a remoteplasma and may be a capacitive-coupled plasma or an inductive-coupledplasma. The heat treatment may include, but is not limited to,subjecting the as-formed thickness of the conformal portion 110 b, 110b′ to an elevated temperature.

The conformal portion 110 b, 110 b′ may be formed at a thicknesssufficient to provide the desired conformality and quality to the liner110, 110′. The conformal portion 110 b, 110 b′ may be formed to adesired thickness, such as from about 20 Å to about 60 Å or from about30 Å to about 50 Å. The conformal portion 110 b, 110 b′ may have asingle (i.e., substantially uniform) thickness. Thus, the liner 110,110′ may have a total thickness of from about 30 Å to about 100 Å, suchas from about 30 Å to about 70 Å. In one embodiment, the conformalportion 110 b, 110 b′ has a substantially constant thickness of about 40Å.

Since the protective portion 110 a, 110 a′ and the conformal portion 110b, 110 b′ may be formed by different techniques, the portions of theliner 110, 110′ may be formed in different chambers. However, if the twoportions of the liner 110, 110′ are formed by similar techniques, theliner 110, 110′ may be formed in a single chamber.

In one embodiment, the protective portion 110 a, 110 a′ is formed of SiNby PECVD and the conformal portion 110 b, 110 b′ is formed of SiN byALD. The SiN of the protective portion 110 a, 110 a′ may differ incomposition (e.g., differing amounts of nitrogen) from the SiN of theconformal portion 110 b, 110 b′ or both portions may have the samecomposition. While the liner 110, 110′ includes both portions composedof SiN, the protective portion 110 a, 110 a′ and the conformal portion110 b, 110 b′ may be visually distinguishable, such as by scanningelectron microscopy (SEM) or tunneling electron microscopy (TEM). Whileboth portions of the liner 110, 110′ are formed of SiN, a moreaggressive deposition technique may be used to form the conformalportion 110 b, 110 b′ since the materials of the stacks 105 are coveredby the protective portion 110 a, 110 a′. In addition, since thematerials of the stacks 105 are covered by the protective portion 110 a,110 a′, the stacks 105 having the liner 110, 110′ may spend a longeramount of time at a higher temperature, such as at a temperature ofgreater than about 250° C., during downstream processing.

In another embodiment, the protective portion 110 a, 110 a′ is formed ofSiN by PECVD and the conformal portion 110 b, 110 b′ is formed of SiOCNby remote plasma CVD. In yet another embodiment, the protective portion110 a, 110 a′ is formed of SiN by PECVD and the conformal portion 110 b,110 b′ is formed of SiCN by direct plasma CVD. In still anotherembodiment, the protective portion 110 a, 110 a′ is formed of SiN byPECVD and the conformal portion 110 b, 110 b′ is formed of SiCN byremote plasma CVD.

The liner 110, 110′ may be configured to include more than two portions,the combination of which may achieve the desired adhesion, protective,step coverage, and film quality characteristics. For instance, the liner110, 110′ may include a third portion (not shown) on the conformalportion 110 b, 110 b′ or in between the protective portion 110 a, 110 a′and the conformal portion 110 b, 110 b′. By way of example only, thethird portion may be formed from a dielectric material having higherthermal insulating properties than the materials of the protectiveportion 110 a, 110 a′ and the conformal portion 110 b, 110 b′.

A method of forming a 3D cross-point memory structure 200 (FIG. 2D)including a liner 210 on the stacks 205 is illustrated in FIGS. 2A to2D. A conductive material 230, bottom electrode material 240, switchingdiode element material 250, middle electrode material 260, phase changematerial 270, top electrode material 280, and hard mask material 290 maybe formed on a substrate 220, as shown in FIG. 2A. The materials may beformed on the substrate 220 by conventional techniques, which are notdescribed in detail herein. The substrate 220 may be a base material orconstruction upon which additional materials are formed. The substrate220 may be a semiconductor substrate, a base semiconductor layer on asupporting structure, a metal electrode or a semiconductor substratehaving one or more layers, structures or regions formed thereon. Thesubstrate 220 may be a conventional silicon substrate or other bulksubstrate comprising a layer of semiconductive material. As used herein,the term “bulk substrate” means and includes not only silicon wafers,but also silicon-on-insulator (“SOI”) substrates, such assilicon-on-sapphire (“SOS”) substrates and silicon-on-glass (“SOG”)substrates, epitaxial layers of silicon on a base semiconductorfoundation, and other semiconductor or optoelectronic materials, such assilicon-germanium, germanium, gallium arsenide, gallium nitride, andindium phosphide. The substrate 220 may be doped or undoped. Thesubstrate 220 may include transistors and/or circuits such as, forexample, decoding circuits of 3D cross-point memory cells.

The conductive material 230 may be formed on the substrate 220. Thebottom electrode material 240 may be formed on the conductive material230. The switching diode element material 250 may be formed on thebottom electrode material 240. The middle electrode material 260 may beformed on the switching diode element material 250. The phase changematerial 270 may be formed on the middle electrode material 260. The topelectrode material 280 may be formed on the phase change material 270and a hard mask material 290 may be formed on the top electrode material280. The hard mask material 290 may be formed of a nitride material,such as silicon nitride. These materials may be formed by conventionaltechniques, which are not described in detail herein.

The conductive material 230 may be a conductive material including, butnot limited to, tungsten, aluminum, copper, nickel, strontium, hafnium,zirconium, titanium, tantalum, platinum, alloys thereof, heavily dopedsemiconductor material, a conductive silicide, a conductive nitride, aconductive carbide, or combinations thereof. In some embodiments, theconductive material 230 is tungsten.

The bottom electrode material 240, the middle electrode material 260,and the top electrode material 280 may be formed from the same ordifferent materials. The electrode materials 240, 260, 280 may be formedfrom a conductive or semiconductive material, such as tungsten,platinum, palladium, tantalum, nickel, titanium nitride (TiN), tantalumnitride (TaN), tungsten nitride (WN), polysilicon, a metal silicide, ora carbon material. In some embodiments, the bottom electrode material240, middle electrode material 260, and the top electrode material 280are formed from a carbon material.

Each of the switching diode element material 250 and the phase changematerial 270 may be formed from a chalcogenide material, such as achalcogenide-metal ion glass, a chalcogenide glass, or other materials.The chalcogenide material may include sulfur, selenium, tellurium,germanium, antimony, or combinations thereof. The chalcogenide materialmay be doped or undoped or may have metal ions mixed therein. By way ofnon-limiting example, the chalcogenide material may be an alloyincluding indium, selenium, tellurium, antimony, arsenic, bismuth,germanium, oxygen, tin, or combinations thereof. The switching diodeelement material 250 and the phase change material 270 may includechalcogenide materials having the same composition or differentcompositions. In some embodiments, the switching diode element material250 and the phase change material 270 comprise different chalcogenidematerials.

Openings 215 may be formed in the materials overlying the substrate 220to expose a top surface 225 of the substrate 220, as shown in FIG. 2B.The openings 215 may be formed by conventional techniques, such as byremoving portions of the underlying materials using the hard maskmaterial 290 as a mask. The hard mask material 290 may be patterned, andthe pattern transferred into the underlying materials using conventionalphotolithography techniques, which are not described in detail herein.The materials exposed through the patterned hard mask 290′ may beremoved by conventional removal techniques, which are not described indetail herein. Each of the materials may be removed separately or asingle etchant may be used to simultaneously remove one or more of thematerials. The patterned hard mask 290′ may be removed, forming stacks205. The stacks 205 include conductive feature 230′ on the substrate220, bottom electrode 240′ on the conductive feature 230′, switchingdiode element 250′ on the bottom electrode 240′, middle electrode 260′on the switching diode element 250′, active storage element 270′ on themiddle electrode 260′, and top electrode 280′ on the active storageelement 270′, which correspond to the conductive feature 130, bottomelectrode 140, switching diode element 150 (e.g., a diode or an ovonicthreshold switch), middle electrode 160, active storage element 170, andtop electrode 180, respectively, in FIGS. 1A and 1B. As shown in FIG.2C, the protective portion 210 a of the liner 210 may be formed on thestacks 205 by a low temperature process, as described above. Theprotective portion 210 a of the liner 210 may be formed on sidewalls ofthe conductive feature 230′, bottom electrode 240′, switching diodeelement 250′, middle electrode 260′, active storage element 270′, andtop electrode 280′, and on a top horizontal surface of the top electrode280′, as well as on the top surface 225 of the substrate 220. As shownin FIG. 2D, the conformal portion 210 b of the liner 210 may then beformed on the protective portion 210 a by a process as described above.The optional treatments described above to improve the quality of theliner 110, 110′ may be conducted after completion of the liner 210 orduring formation of the liner 210.

If the liner 110, 110′ includes a third portion (not shown), the thirdportion may be formed by similar techniques to those described above forthe protective portion 110 a, 110 a′ and the conformal portion 110 b,110 b′. The third portion may be formed on the conformal portion 110 b,110 b′ or in between the protective portion 110 a, 110 a′ and theconformal portion 110 b, 110 b′.

Accordingly, a method of forming a semiconductor structure is disclosed.The method comprises forming a protective portion of a liner on at leasta portion of stack structures on a substrate. The protective portioncomprises a material formulated to adhere to the stack structures. Aconformal portion of the liner is formed on the protective portion or onthe protective portion and exposed materials of the stack structures. Atleast one of the protective portion and the conformal portion does notcomprise aluminum.

Another method of forming a semiconductor structure is also disclosed.The method comprises forming a protective portion of a liner on stackstructures on a substrate. The protective portion comprises siliconnitride or aluminum oxide. A conformal portion of the liner is formed onthe protective portion. The conformal portion comprises a materialselected from the group consisting of silicon nitride, siliconoxynitride, silicon carbonitride, silicon carboxynitride, and silicondioxide.

The openings 215 between adjacent stacks 205 may be filled with adielectric material 235, such as a silicon dioxide material, as shown inFIG. 2E. Additional process acts may then be conducted to form acomplete 3D cross-point memory structure from the structure 200 in FIGS.2D and 2E. The additional process acts may be formed by conventionaltechniques, which are not described in detail herein.

Another method of forming a 3D cross-point memory structure 200′including the liner 210′ on the stacks 205 is illustrated in FIGS. 2Fand 2G. Rather than forming the protective portion 210 a of the liner210 on the entire stacks 205 as shown in FIG. 2C, the protective portion210 a′ may be formed only on materials that are sensitive to heat orchemical damage, such as on the chalcogenide or carbon materials. By wayof example only, the protective portion 210 a′ of the liner 210′ may beformed on sidewalls of the switching diode element 250′, middleelectrode 260′, active storage element 270′, and top electrode 280′, andon a top horizontal surface of the top electrode 280′, as shown in FIG.2F. The conformal portion 210 b′ of the liner 210′ may then be formed onthe protective portion 210 a′, and on sidewalls of the conductivefeature 230′, bottom electrode 240′, switching diode element 250′,middle electrode 260′, active storage element 270′, and top electrode280′, and on the top horizontal surface of the top electrode 280′, aswell as on the top surface 225 of the substrate 220, as shown in FIG.2F. The optional treatments described above to improve the quality ofthe liner 110, 110′ may be conducted after completion of the liner 210′or during formation of the liner 210′.

The openings 215 between adjacent stacks 205 may be filled with thedielectric material 235, such as a silicon dioxide material, asdescribed above in reference to FIG. 2E. Additional process acts maythen be conducted to form a complete 3D cross-point memory structurefrom the structures in FIG. 2G. The additional process acts may beformed by conventional techniques, which are not described in detailherein.

While the liner 110, 110′, 210, 210′ is described and illustrated hereinas being used in cross-point memory structures 200, 200′, the liner 110,110′, 210, 210′ according to embodiments of the present disclosure maybe used in other semiconductor structures where sensitive materials,such as chalcogenide or carbon materials, are present in high aspectratio features and need protection from downstream processing acts.

The liner according to some embodiments of the present disclosure mayexhibit improved step coverage compared to that of a single materialliner (an oxide liner) formed by PECVD. The step coverage of a linerincluding SiN formed by PECVD as the protective portion and SiN formedby ALD as the conformal portion was measured by conventional techniques,which are not described in detail herein. It was determined that theliner exhibited about 80% step coverage (e.g., conformality) compared tothe single material liner (the oxide liner) formed by PECVD, whichexhibited about 30% step coverage. Without being bound by any theory,the improved step coverage of the liner according to some embodiments ofthe present disclosure is believed to be due to the high step coverageprovided by the conformal portion of the liner.

Accordingly, disclosed is a semiconductor structure comprising stackstructures and a liner comprising a protective portion and a conformalportion on at least a portion of the stack structures. The stackstructures comprise carbon materials and chalcogenide materials on asubstrate. The liner exhibits about 80% step coverage.

The liner according to some embodiments of the present disclosure alsoexhibited improved adhesion to carbon materials compared to that of asingle material liner formed from an oxide or a carbon-containingnitride. The liner included SiN formed by PECVD as the protectiveportion and SiN formed by ALD as the conformal portion. The adhesion wasmeasured by a blanket PVD carbon tape test, a 4-point bend interfacialfracture energy test, SEM structural verification, and/or TEM structuralverification. These tests are known in the art and, therefore, are notdescribed in detail herein. The liner exhibited an interfacial fractureenergy of greater than or equal to about 3 J/m², such as greater than orequal to about 20 J/m² for adhesion between the PVD carbon and theliner. With the single material liner, delamination from the carbonmaterials of the electrodes was observed, which resulted in diffusionand migration of the chalcogenide materials. The single material liner,which was formed from an oxide or a carbon-containing nitride, exhibitedan interfacial fracture energy of less than 2.8 J/m² for adhesionbetween the PVD carbon and the oxide.

Accordingly, disclosed is a semiconductor structure comprising stackstructures and a liner comprising a protective portion and a conformalportion on at least a portion of the stack structures. The stackstructures comprise electrode materials and chalcogenide materials on asubstrate. The liner exhibits an interfacial fracture energy of greaterthan or equal to about 3 J/m² between the protective portion of theliner and the stack structures.

While certain illustrative embodiments have been described in connectionwith the figures, those of ordinary skill in the art will recognize andappreciate that embodiments encompassed by the disclosure are notlimited to those embodiments explicitly shown and described herein.Rather, many additions, deletions, and modifications to the embodimentsdescribed herein may be made without departing from the scope ofembodiments encompassed by the disclosure, such as those hereinafterclaimed, including legal equivalents. In addition, features from onedisclosed embodiment may be combined with features of another disclosedembodiment while still being encompassed within the scope of thedisclosure as contemplated by the inventors.

What is claimed is:
 1. A method of forming a device, the methodcomprising: forming a protective portion of a liner adjacent to stackscomprising chalcogenide materials and carbon materials, the protectiveportion comprising silicon nitride or aluminum oxide and the protectiveportion exhibiting a varying thickness; and forming a conformal portionof the liner adjacent to the protective portion, the conformal portioncomprising silicon nitride, silicon oxynitride, silicon carbonitride,silicon carboxynitride, or silicon dioxide.
 2. The method of claim 1,wherein forming a protective portion of a liner adjacent to stackscomprising chalcogenide materials and carbon materials comprises formingthe protective portion of the liner on a top surface and on at least aportion of sidewalls of the stacks.
 3. The method of claim 1, whereinforming a protective portion of a liner adjacent to stacks comprisingchalcogenide materials and carbon materials comprises forming theprotective portion of the liner as a continuous material over thestacks.
 4. The method of claim 1, wherein forming a protective portionof a liner adjacent to stacks comprising chalcogenide materials andcarbon materials comprises forming the protective portion directlycontacting the stacks.
 5. The method of claim 1, wherein forming aprotective portion of a liner adjacent to stacks comprising chalcogenidematerials and carbon materials comprises forming the protective portionby a pulsed plasma enhanced chemical vapor deposition (CVD) process. 6.The method of claim 1, wherein forming a protective portion of a lineradjacent to stacks comprising chalcogenide materials and carbonmaterials comprises forming a silicon nitride protective portion using anon-chlorinated reagent.
 7. The method of claim 1, wherein forming aconformal portion of the liner adjacent to the protective portioncomprises forming the conformal portion directly contacting theprotective portion.
 8. The method of claim 1, wherein forming aconformal portion of the liner adjacent to the protective portioncomprises forming the conformal portion by atomic layer deposition.
 9. Amethod of forming a device, comprising: forming a protective portion ofa liner on stacks at a temperature of less than about 250° C., theprotective portion comprising silicon nitride or aluminum oxide and thestacks comprising one or more of chalcogenide materials and carbonmaterials; and forming a conformal portion of the liner on theprotective portion at a temperature greater than the temperature used toform the protective portion, the conformal portion comprising siliconnitride, silicon oxynitride, silicon carbonitride, siliconcarboxynitride, or aluminum oxide.
 10. The method of claim 9, whereinforming a protective portion of a liner on stacks comprises conformallyforming the protective portion at a substantially uniform thickness onthe stacks.
 11. The method of claim 9, wherein forming a protectiveportion of a liner on stacks comprises conformally forming aluminumoxide on the stacks.
 12. The method of claim 9, wherein forming aconformal portion of the liner on the protective portion comprisesforming the conformal portion at a temperature of greater than about250° C.
 13. The method of claim 9, wherein forming a conformal portionof the liner on the protective portion comprises forming the conformalportion and the protective portion to exhibit a substantially uniformtotal thickness.
 14. A method of forming a device, comprising: forming aprotective portion of a liner adjacent to stacks at a temperature ofless than about 250° C., the protective portion comprising siliconnitride or aluminum oxide and the stacks comprising one or morechalcogenide materials; and forming a conformal portion of the lineradjacent to the protective portion, the conformal portion comprisingsilicon nitride, silicon oxynitride, silicon carbonitride, siliconcarboxynitride, or aluminum oxide.
 15. The method of claim 14, whereinforming a protective portion of a liner adjacent to stacks comprisesforming the protective portion on at least a portion of the stacks. 16.The method of claim 14, wherein forming a protective portion of a lineradjacent to stacks comprises forming the protective portion at a greaterthickness on a horizontal surface of the stacks and on upper sidewallsof the stacks and at a lower thickness on lower sidewalls of the stacks.17. The method of claim 16, wherein forming a conformal portion of theliner adjacent to the protective portion comprises forming the conformalportion directly contacting the protective portion and directlycontacting a portion of the stacks.
 18. The method of claim 14, whereinforming a conformal portion of the liner adjacent to the protectiveportion comprises forming the conformal portion directly contacting theprotective portion.
 19. The method of claim 14, wherein forming aconformal portion of the liner adjacent to the protective portioncomprises forming the conformal portion comprising silicon nitrideadjacent to the protective portion comprising silicon carboxynitride.20. The method of claim 14, wherein: forming a protective portion of aliner adjacent to stacks comprises forming the protective portioncomprising silicon nitride by a plasma enhanced chemical vapordeposition process; and forming a conformal portion of the lineradjacent to the protective portion comprises forming the conformalportion comprising silicon carbonitride by direct plasma CVD.